JPS60210555A - Mortar composition for spray - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a concrete or mortar composition for blowing.

Conventionally, conch for spraying! J-)-1' or as a mortar composition, a water-soluble polymer thickener such as polyvinyl alcohol, polyacrylamide, sodium polyacrylate, or polyethine oxide? Some were added to concrete or mortar (Japanese Patent Application Laid-open No. 57-185759, No. 5)
7-201498 publications).

These materials had problems such as high viscosity and difficulty in construction.

There is also an aqueous dispersion made by completely crosslinking a cellulose ether thickening agent (Japanese Patent Application Laid-Open No. 58-185463), but this has the problem that it does not have the strength of concrete.

Did the inventors have such a problem? As a result of research to solve this problem, Eisai has arrived at the present invention. That is, the present invention uses Vinyl/L/ME combined emulsion (a), cement (b), and aggregate (c) whose pure content has an acid value within the range of 100 to 500.
and, if necessary, water (d) for blowing concrete.
1 or Morta/Shi composition.

The polymer emulsion (a) used in the present invention includes a polymer composed of a carboxyl group-containing monomer and other monomers.

The monomers containing calboxoxy p group include the following and the following.
(2) Unsaturated polycarboxylic acids maleic acid, itaconic acid, fumaric acid, etc. Among these, preferred are acrylic acid, methacrylic acid, maleic acid and itaconic acid, and particularly preferred is methacrylic acid.

Other monomers include two or more of the following ν and .

(11g aqueous monomer (a) unsaturated carboxylic acid ester (meth)acrylic acid alekyl (alkyl group) R prime number is 1 to 12) ester [(meth)acrylic acid methyl-
, ethylhexyl, n- or isopropyl-, n- or isobutyl-, 2-ethylhexyl-
Itaconic acid dieste Jv+
Diesters of maleic acid, etc. (b) Aromatic vinyl monomers, styrene, etc. (c) Vinyl esters, vinyl acetate, etc.) Unsaturated nitrites ) Halogen-containing monomers, hinyl chloride, chloroprenat (2) Hydrophilic monomers without acid value, amide thread-containing monomers [(meth)acrylamide] (a small amount may be used), etc. Preferred among these are alkyl esters of (meth)acrylic acid.

Is the above polymer a crosslinking monomer (crosslinking agent) if necessary? Examples of the crosslinking agent include compounds having at least two polymerizable divalent bonds, such as the following and two or more of these.

(1) Di- or polyvinyl compounds such as divinylbenzene, divinyl-reto-renine, divinylquinrene, divinylethe-I, divinylketone, trivinylbenzene, etc. (2) Di- or polyesters of unsaturated mono- or polycarboxylic acids and polyol-I. Polyol (ethylene glycol/L'l)! I methylolpropane, glycerin, polyethylene glycol,
(Holipropylene recorder, etc.)
(meth)acrylic acid esters such as di(meth)acrylate of ethylene glycol (3) Di- or polyallyl esters of polycarboxylic acids such as diallyl fumarphthalate (4) Bis(meth)acrylic acid amide N,N-methyl In addition, crosslinking agents having at least two (2) lift polymerizable divalent bonds can also be used, such as polyvinyl bis(meth)acrylamide and the like, as described in US Pat. No. 4,076,668.

Among these, preferred is Gibini I retoluene.

These are diallyl maleate, diallyl phthalate, and polyethylene glycol diacrylate.

In the polymer, the content of carboxy/silicone group-containing monomer (7) is usually from 20 to 75%, preferably from 30 to 70%, based on the weight of the total monomers. The content of hydrophobic monomers is usually 25 to 80 g, preferably 3 g, based on the weight of total monomers.
It is 0-70%.

The weight ratio of the hydrophilic monomer having no acid value to the monomer containing a carboxy I group is usually 0:100 to 50:50, preferably O:100 to 25Nia5.

The content of crosslinking agent is usually θ~2 based on the weight of total monomers.
H, preferably 0 to 1 H.

Polymer emulsion consists of monomer and water? It can be obtained by mixing, emulsifying or dispersing and polymerizing using an emulsifier.

Examples of emulsifiers used for emulsification or dispersion include anionic emulsifiers such as sulfate ester salts (7/L"
f/L' sulfate ester salt, polyoxyethylene alkyl sulfate ester salt, polyoxyethylenoalkylphenyl sulfate ester salt, etc.), sulfonic acid 1. n (argylbenzene sulfonate).

Phosphate ester salt (argyl phosphate ester salt.

polyoxyethylene alkyl phosphate ester salt, etc.)・
and higher fatty acid salts, and nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl 7-lephenyl ether, and polyoxyethylene alkyl fatty acid ester are used alone or in combination of two or more.

Among these, preferred are polyoxyethylene alkyl phenyl sulfate and polyoxyethylene alkyl ether sulfate.

The amount of emulsifier used is usually 0.5 to 0.5 based on the monomer weight sensitivity.
IO%, preferably 1 to 5φ.

Monomer, emulsifier, and water as methods for emulsifying and dispersing? How to add and stir, monomer and emulsifier r pre-mixed, water? Learn how to add and stir. The stirring temperature is usually 0 to 70°C.

As the stirring device, a conventional stirring device such as a propeller stirrer, a homogenizer, a straight mixer, etc. can be used.

Polymerization methods include methods that use polymerization catalysts, ultraviolet rays, radiation, etc. I like the way you use it.

If polymerized, is all or most of the claw body (e.g. 80 Sokei'2)? In the method of charging a reaction vessel and polymerizing it (so-called batch charging polymerization), a part of the monomer mixture (and λ
(less than 80)? Pre-prepared leftover monomer mixture?
Compared to continuous or divided addition methods, this method is preferable because stable polymerization can be carried out without producing a large amount of coagulated material during polymerization.

Examples of polymerization catalysts include persulfates (sodium salts, potassium salts, ammonium salts, etc.) and peroxides ([-butyl hydroperoxide, sodium peroxide).

Redox catalysts (peroxides or persulfates/reducing agents such as potassium persulfate/sodium sulfite.

Hydrogen peroxide/ferrous salts etc. are used. Among these, the most advantageous are redox catalysts.

The amount of catalyst to be used is usually 0.01 to 0.05% by weight T: based on the entire simple substance. Polymerization initiation temperature is usually 20 to 80°C, preferably 1
Preferably, the temperature is 3o-70°C. Polymerization initiation temperature is 800? When the temperature exceeds λ, the degree of polymerization decreases by 2 degrees, and when the temperature is lower than 20°C, the polymerization progresses and separates. The degree of weight is usually 20-80c, preferably 3
The temperature is 0 to 80°C.

Note that the pure acid value of the polymer emulsion is 100 to 500.
It is manufactured so that one song is 100 to 5 from the beginning.
In addition to the method of manufacturing so that it becomes 00, is it possible to neutralize it with alkali to increase the acid value? It may be prepared as above (in the form of partial salt).

The resulting polymer emulsion has a solid content concentration of heavy Jt.
It is usually 15 to 40%, preferably 20 to 80% on a standard basis. Polymer emulsion viscosity is typically 8”-20 cps
(80c% B-type viscometer, measured at 12 times per minute).

The acid value of the pure component (polymer) in the polymer emulsion is 100
~500. Preferably 200-45o.

Particularly preferably 250 to 400. Acid value is 100
Gum up due to contact with cement in Yoneman? If the number exceeds 500, it becomes difficult to form a stable polymer emulsion.

The viscosity of the polymer in the polymer emulsion is such that the viscosity of a one-line aqueous solution after neutralization with sodium hydroxide is usually 100 cps or more, preferably 300 cps (p5 or more?).

Cement used in the present invention includes ordinary Portland cement, other Portland cements (early strength, ultra early strength, moderate heat, white Portland cement, etc.), mixed Portland cement (blast furnace cement, fly ash cement, silica cement, etc.) Gadokaagera will be saved.

Examples of the aggregate used in the present invention include river sand, sea sand, mountain sand, chestnut stone, crushed stone, and fly ash. Fine aggregates are usually used for mortar, and coarse and fine aggregates are used for concrete.

In the composition of the present invention, a vinyl polymer emulsion (
(7) (a)) The blending amount for (b) is usually 0001 to 5 on a weight basis as a pure polymer, preferably 001
~1ch. The blending amount is 0. If OO is less than 1%, the amount of dust generated and the splashing effect of concrete or mortar from the target wall will be insufficient, and the effect of reducing the amount of dust generated will be insufficient. If it is exceeded, the viscosity of the mortar or concrete composition will become too high, and the liquid resistance will increase, making it difficult to spray.

The amount of aggregate is usually 1:2 to 1:4 in the weight ratio of cement to fine aggregate in the case of mortar spraying, and the weight ratio of cement Y fine aggregate and coarse aggregate in the case of concrete spraying. The ratio is usually 1:2:1 to 1:5:20.

The amount of water is usually 45-50% for mortar, and usually 4% for concrete spraying.
It is 0 to 45 chi.

The composition of the present invention consists of seven ingredients (b), aggregate (c) and, if necessary, water (d). It can be obtained by adding vinyl IV polymer emulsion (a) k at any stage of preparation. For example, mix (a) and (c) in advance and then (d)? A method of adding (a) to (a) after preparing a dry kneaded mixture of (C) and (b), a method of adding (a) to (d)
) Examples include a method of dispersing K and then adding it to (b) and (C). The method of adding after dispersing (d) and (a)' has the greatest dust generation prevention effect.

When using the composition of the present invention for spraying, wet methods and dry methods can be used as spraying methods. The former is cement
Aggregate and water materials? After mixing in a mixer for 90 minutes, the mixture is compressed with compressed air and sprayed through a nozzle. You can also use Ruizu's method, which involves spraying while merging.

The composition of the present invention includes the above (aL (b), (C),
In addition to component (d), cement quick setting agents for accelerating the hardening of cement, such as sodium aluminate, potassium aluminate, water glass, soda carbonate, sodium sulfate, organic acid soda, calcium chloride, and aluminum sulfate.

Calcium apinate, calcium haloaluminate,
Tub may be added with triethanolamine, etc. Kon
Preferred among these are potassium aluminate and calcium haloaluminate.

The addition of such quick setting agents prevents the cement composition from sagging,
It is preferred from the viewpoint of quick hardening and improved resistance to water leakage, and is particularly preferred for construction inside tunnels. The amount of cement quick setting agent added is usually 0 to 1 based on the weight of cement.
0 inches, preferably 0 to 7 inches.

Also, if necessary, dispersion stability of mortar or concrete? Dispersion stabilizer (bentonite, CMC, etc.) to increase cement hardening? Cement retarder for retarding (
(glyconic acid, citric acid, gypsum, various sugars, etc.); fillers, anti-shrinkage agents; anti-crank agents (organic, inorganic fibers, etc.)? It may be added as appropriate. In the case of a cement retarder, the amount added is usually 0 to 10% relative to the cement weight, and in the case of a dispersant, it is usually θ to 5%.

Ippa 5 →ΦNose disputeΦ.

In addition, fluidizing agents (lignin-based sulfonates, melamine-based sulfonates, polycyclic aromatic sulfonates, naphthalene-based sulfonates); penetrants (polyoxine ethylene alkyl ether, polyoxy7 ethylene alkyl phenyl ether, Alkyl sulfosuccinates, fluorine-based surfactants, silicone-based surfactants, etc.) can also be added as appropriate.

The amount added is usually 0 to 5% in the case of a fluidizing agent and .theta. to 5% in the case of a penetrant, based on the weight of cement.

The composition of the present invention exhibits the following effects compared to conventional compositions.

In other words, conventional sodium polyacrylate, polyvinyl alcohol, polyacrylamide, etc. added to concrete or mortar in the form of an aqueous solution (6) have a high viscosity and are difficult to apply, and they also have a powdery form. When C'C is added, the development of viscosity is slow, resulting in increased dust generation and 7'+5.The composition of the present invention has a low viscosity and is extremely easy to apply. However, when it comes into contact with an alkali such as cement, the viscosity increases immediately and dust is generated.
No problems such as in.

Also, polyethylene ogizide, polyvinylal]-tV
, Ho [acrylamide, cellulose ether rolled tobacco n
"Moisture tf &'FR'tlconcrete"
l ft is concrete added to molar tar.
The strength of the water, especially the initial strength, is particularly low, and precipitation occurs due to contact with polyvalent metal salts in cement, and the hose blowing causes gum up inside the rock. However, does the composition of the present invention improve concrete strength? Improve and also gum up? I won't wake you up.

Also, does spraying have the effect of suppressing the generation of dust during work and the splashing of concrete or mortar from the target wall? It can also contribute to improving the working environment.

Because of these effects, the composition of the present invention has excellent power in spraying work for tunnels, etc. Demonstrate. ′ = Is it also effective for blowing down on underground structures, spring water surfaces, and wet surfaces? Demonstrate.

The present invention will be further explained below with reference to Examples, but the present invention is not limited to these specific examples.

Production examples 1 to 4. Comparative Production Examples 1 and 2 (Production of Vinyl Polymer Emulsion) A mixture of water 6507, polyoxyethene sodium alkylphenol sulfate 122, and the monomers shown in Table 1 was placed in a glass kolben with stirring rack for 25 hours, nitrogen. While introducing r, the temperature was adjusted to 50C and emulsified.

Then sodium persulfate and sodium sulfite as heavy catalysts? 207 ml of each 2% solution was added. After polymerization starts, the polymerization humidity rises to 70-75℃, but after reaching the maximum temperature, Kolben? After cooling, when the temperature reached 50°C, 20% of each polymerization catalyst was added again, and the mixture was aged for 2 hours to consume the unreacted monomers.Then, the contents were washed with a cloth. I asked if it was a military combination emulsion.

Table 1 During the US military conflict, the entire contents became highly viscous, and eventually the emulsion itself broke down.

Example 1゜ A molcle composition having the formulation shown below was obtained.

Mortar composition <per 1i) Ordinary Portland cement: 470Kg fine aggregate (river sand)
:1410 to 7 This composition? Used for dry-sprayed rock made by Alipar ■ “Aliper 2”
One crack was constructed on the inner surface of a tunnel with a diameter of 2 m using the ``60 type''.

For blowing, use a premix of cement, fine bone 41, and Cemenod quick-setting agent, and a mixture of vinyl vehicle chassis Emulshore 2 from Manufacturing Example 1 and water. How to remove the blow after mixing for 1-2 seconds? used.

The dust generation area was measured using a digital dust meter at a location 1 m downwind from the spray gun after the start of the blowing f dimension.

In addition, the mortar penetration resistance edge sound was measured using a Brokku penetration test device. In addition, the compressive strength of mortar at each material age was determined to be 711u according to 2JISA-1108.

The results obtained are shown in Table 2.

On the other hand, in the vinyl/I/polymer emulsion 7 04%/mortar blend system with cement added in FFU Preparation Example 1, 1
When the spraying machine was disassembled after continuous spraying for a period of time, no polymer precipitation was detected.

Example 2 A mortar composition was obtained in the same manner as in Example 1, except that the vinyl composite emulsion of Production Examples 2, 3 or 4 was added with α4/cement, and it was sprayed in the same manner as in Example 1. carried out. The results obtained are shown in Table 3.

Table 3 Comparative Example 1 In place of the emulsion of Production Example 1, the vinyl polymer emulsilone of Comparative Production Example 1, a 1% aqueous solution of polyethylene oxide with a molecular weight of 1.5 million (prepared by stirring in a dissolution tank for about 3 hours), and hydroxyethyl Aqueous solution of cellulose (
(Created by stirring in a dissolution tank for about 2 hours) A mortar composition was obtained in the same manner as in Example 1, except that the amount of cement added was 0.1% pure. The entire blowing process was carried out in the same manner as in Example 1 using this product. The obtained f'L is shown in Table 4.

Table 4 Also, how many examples of JM-made mortar and hydroxyethyl cellulose were added? After blowing the added mortarke for 1 hour continuously, is it possible to blow? When they were disassembled, a considerable amount of grayish-white condensation (mostly organic polymer compounds) was found to be attached to the inner walls of both cases. Manabu Shiga, Commissioner of the Japan Patent Office, Patent Application No. 40750 filed in 19822, Title of the invention, 3, Relationship with the case of the person making the amendment, Voluntary action by the patent applicant5, Number of inventions increased by the amendment6, Subject of the amendment Column 7 of "Detailed Description of the Invention" of the specification, contents of the amendment as shown in attached sheet 1), page 12, line 1 of the specification. For example, write a statement like (a) and (C)...''. For example, correct (a>, (b), and (C) to ``Oh...'').

Claims (1)

[Claims] 1. Vinyl whose pure acid value is within the range of 100 to 500.
! A concrete or mortar composition for spraying consisting of a combined emulsion (a), cement (b) + aggregate (C) and optionally water (d). 2. The weight of (a) relative to (b) is 0 as the body purity,
The composition according to claim 1, which is OO1-5. 3. The composition according to claim 1 or 2, wherein the polymer is a polymer of methacrylic acid and an alkyl/l/(alkyl group carbon g number 1 to 4) ester of methacrylic acid and (meth)acrylic acid. .